Segmented enrichment and recovery method for lithium-containing porcelain clay ore co-associated with rubidium and cesium

Abstract

The invention relates to the technical field of mineral separation, and provides a segmented enrichment and recovery method for lithium-containing porcelain clay ore co-associated with rubidium and cesium, which comprises the following steps: grinding the lithium-containing porcelain clay ore to obtain ground ore pulp; the ore grinding pulp is subjected to sedimentation desliming, and settled sand and slime are obtained; the settled sand is subjected to size mixing, and to-be-separated ore pulp is obtained; lepidolite flotation is conducted on the to-be-separated ore pulp through a lepidolite collecting agent, and lithium separation tailings and lepidolite concentrate containing rubidium and cesium are obtained; carrying out potassium feldspar flotation on the lithium separation tailings by adopting a potassium feldspar collecting agent to obtain re-separation tailings and potassium feldspar concentrate containing rubidium and cesium; and fluoride-free separation of feldspar and quartz is conducted on the recleaning tailings, and feldspar concentrate and quartz concentrate are obtained. According to the segmented enrichment and recovery method provided by the invention, comprehensive utilization of co-associated rubidium and cesium in the ore can be realized to the greatest extent while the recovery of the main utilization mineral lepidolite is preferentially ensured, and qualified feldspar products and quartz products are obtained.

Description

Technical Field

[0001] This disclosure relates to the field of mineral processing technology, specifically to a method for the staged enrichment and recovery of lithium-bearing kaolin ore containing rubidium and cesium. Background Technology

[0002] Lithium-bearing kaolin is an ideal ceramic raw material. The ore contains rare metals such as lithium, rubidium, cesium, niobium, and tantalum, giving it significant economic value. The main mineral components of lithium-bearing kaolin include quartz, feldspar, and mica, with a small amount of kaolinite. It is frequently used in the ceramics and glass industries.

[0003] Currently, the beneficiation process for lithium-bearing kaolin ore is mainly based on flotation. Flotation typically uses a combination of cationic and anionic collectors, primarily dodecylamine and oxidized paraffin soap, with a lithium recovery rate of 70%–75%. However, although this flotation method can achieve lithium recovery, the lithium recovery rate is low, especially since the abundant rubidium, cesium, quartz, and feldspar resources in lithium-bearing kaolin ore have not been specifically recovered and utilized; in particular, the rubidium and cesium recovery rate in lithium-bearing kaolin ore is only 40%–50%.

[0004] In summary, there is an urgent need for a method that can not only improve the lithium recovery rate of lithium-bearing kaolin ore, but also enhance the comprehensive recycling and utilization of rubidium, cesium, quartz and feldspar resources. Summary of the Invention

[0005] The purpose of this disclosure is to overcome the shortcomings of the prior art and provide a segmented enrichment and recovery method for lithium-bearing kaolin ore containing rubidium and cesium, so as to at least achieve the effect of maximizing the comprehensive utilization of rubidium and cesium in the ore while prioritizing the recovery of the main mineral lepidolite, and obtaining qualified feldspar and quartz products.

[0006] The purpose of this disclosure is achieved through the following technical solution:

[0007] On the one hand, a method for staged enrichment and recovery of lithium-bearing kaolin ore containing associated rubidium and cesium is provided. The staged enrichment and recovery method includes: grinding the lithium-bearing kaolin ore to obtain a grinding slurry; settling and desliming the grinding slurry to obtain sand and slime; conditioning the sand to obtain a slurry to be processed; performing lepidolite flotation on the slurry to obtain lithium tailings and rubidium- and cesium-containing lepidolite concentrate using a lepidolite collector; performing potassium feldspar flotation on the lithium tailings using a potassium feldspar collector to obtain reprocessing tailings and rubidium- and cesium-containing potassium feldspar concentrate; and performing fluorine-free separation of feldspar and quartz on the reprocessing tailings to obtain feldspar concentrate and quartz concentrate.

[0008] It is understandable that in the aforementioned lithium-bearing kaolin ore, rubidium and cesium are mainly found in muscovite and potassium feldspar, with muscovite being the predominant species. In addition, potassium feldspar and sodium feldspar coexist in the aforementioned lithium-bearing kaolin ore, both belonging to the feldspar group of minerals; specifically, in the crystal structure of potassium feldspar, aluminum ions (Al...) are present... 3+ ) tends to replace silicon ions (Si) in silicon-oxygen tetrahedra. 4+ This forms [AlO4]. 5- In order to maintain charge balance, the large potassium (K) ion in the structure... + The aluminum ions (Al) are located in larger voids; similarly, in the crystal structure of albite, aluminum ions (Al) are also present. 3+ ) to replace silicon ions (Si) in silicon-oxygen tetrahedra 4+ This forms [AlO4]. 5- The unit differs in that, in order to maintain charge balance, it consists of smaller sodium ions (Na+). + Charge compensation is performed. Therefore, it can be concluded that sodium ions (Na...) + The binding of potassium ions to the crystal lattice relative to potassium ions (K + It is more tightly bound to the crystal lattice.

[0009] It should be noted that the principle of the segmented enrichment and recovery method provided in this disclosure includes: First, using the lepidolite collector, the ore slurry to be processed is subjected to lepidolite flotation to obtain the rubidium-cesium-containing lepidolite concentrate (which can be used as the main mineral for mine development); then, using the potassium feldspar collector, the lithium tailings obtained from the lepidolite flotation are subjected to potassium feldspar flotation to obtain the rubidium-cesium-containing potassium feldspar concentrate (mainly potassium feldspar); finally, the reprocessing tailings obtained from the potassium feldspar flotation are subjected to fluorine-free separation of feldspar and quartz to obtain the quartz concentrate and the feldspar concentrate (mainly sodium feldspar). The acquisition of the rubidium-cesium-containing lepidolite concentrate prioritizes the recovery of the main mineral, lepidolite; the acquisition of the rubidium-cesium-containing lepidolite concentrate and the rubidium-cesium-containing potassium feldspar concentrate achieves the comprehensive utilization of rubidium and cesium co-occurring in the ore; and the acquisition of the quartz concentrate and the feldspar concentrate achieves tailings-free development and utilization of the mine.

[0010] It is worth noting that the segmented enrichment and recovery method provided in this disclosure does not require the addition of any other flotation reagents. Under neutral conditions, the rubidium- and cesium-containing rubidium- and cesium-containing potassium feldspar concentrate can be obtained by using only the lepidolite collector and the potassium feldspar collector, which are two highly selective flotation reagents.

[0011] In some embodiments, the raw materials of the lepidolite collector, by weight, include 40-50 parts of polyetheramine, 20-40 parts of cottonseed oil fatty acid, 5-10 parts of sodium hydroxide, 5-10 parts of glycerol, and 10-20 parts of sodium petroleum sulfonate.

[0012] It is understood that the lepidolite collector is an anionic or cationic collector, and the cationic collector in this anionic or cationic collector is the polyetheramine. Furthermore, it should be emphasized that the hydroxyl group of the polyetheramine gives it superior solubility compared to amines; in addition, the ether functional group of the polyetheramine increases the probability of chelation with lithium, thereby increasing the collecting capacity. Simultaneously, the presence of the ether bond increases the flexibility and hydrophobicity of the molecule, allowing it to better adhere to the surface of lepidolite, thus achieving efficient collection of lepidolite.

[0013] It is worth noting that there is a synergistic effect between the glycerol and the sodium petroleum sulfonate in the lepidolite collector, specifically including: the sodium petroleum sulfonate is a typical anionic surfactant, whose molecular structure contains hydrophilic sulfonic acid groups (-SO3). - The sodium petroleum sulfonate contains lipophilic long-chain hydrocarbon groups. These groups selectively adhere to the target mineral surface via physical adsorption (e.g., van der Waals forces), making the target mineral surface more hydrophobic and thus more easily attached to air bubbles. The bubbles carry the mineral to the surface of the slurry, forming concentrate foam and achieving separation from gangue minerals. Furthermore, glycerol plays an auxiliary role, utilizing its unique physicochemical properties (e.g., water solubility, viscosity adjustment, low freezing point, and mild solvent properties) to further improve the foam brittleness and low-temperature resistance of the lepidol collector. This results in the lepidol collector exhibiting good solubility at room temperature and excellent adaptability to the temperature of the flotation slurry.

[0014] Therefore, the lepidolite collector is suitable for low-grade lithium-bearing kaolin ore, and can achieve efficient collection of lepidolite, thereby ensuring the grade and recovery rate of lithium in the lepidolite concentrate. At the same time, the lepidolite collector not only has good solubility at room temperature, but also has good adaptability to the temperature of flotation pulp. In addition, the lepidolite collector also has the advantages of good stability, simple reagent preparation and application process.

[0015] In some embodiments, the amount of the lepidolite collector used is 300-600 g / t of raw ore.

[0016] In some examples, the lithium mica flotation employs a closed-loop flotation process consisting of one coarse flotation stage, one scavenging stage, and two fine flotation stages.

[0017] It should be noted that there are various methods for preparing the lepidolite collector, and those skilled in the art can make an appropriate selection as needed. This disclosure does not impose any restrictions on this method.

[0018] In some examples, the preparation method of the lepidolite collector includes: mixing the cottonseed oil fatty acid, the sodium hydroxide and water, and carrying out a saponification reaction to obtain saponified fatty acid; mixing the glycerol and the sodium petroleum sulfonate evenly to obtain a modifier; and mixing the polyetheramine, the saponified fatty acid and the modifier evenly to obtain the lepidolite collector.

[0019] For example, the saponification reaction is carried out at a temperature of 70–90°C and for a time of 30–45 minutes.

[0020] For example, the mass ratio of the cottonseed oil fatty acid to the water is 1-2:0.5-2.

[0021] For example, the step of mixing the glycerol and the sodium petroleum sulfonate uniformly includes: mixing the glycerol and the sodium petroleum sulfonate and stirring at a constant temperature.

[0022] For example, the constant temperature is 60–85°C, and the stirring time is 30–45 min.

[0023] For example, the mass ratio of the polyetheramine, the saponified fatty acid and the modifier is 1-2:1-2:0.2-0.3.

[0024] For example, the step of mixing the polyetheramine, the saponified fatty acid and the modifier uniformly includes: mixing the polyetheramine, the saponified fatty acid and the modifier and stirring.

[0025] For example, the stirring time is 30 to 45 minutes.

[0026] In some embodiments, the potassium feldspar collector comprises, by weight, 40-60 parts soybean oil oleic acid, 10-20 parts white oil, 5-10 parts sodium hydroxide, 15-30 parts tributyl phosphate, and 10-20 parts polypropylene glycol monobutyl ether.

[0027] It should be noted that the potassium feldspar collector can perform characteristic adsorption and collection of potassium feldspar in the lithium-containing kaolin ore, but its selective collection ability for sodium feldspar is relatively weak. This is because the anionic complex components such as soybean oil oleic acid and white oil in the potassium feldspar collector will preferentially adsorb on the surface of potassium feldspar, thus exhibiting a preferential flotation effect on potassium feldspar.

[0028] In some embodiments, the amount of potassium feldspar collector used is 100-300 g / t of raw ore.

[0029] In some examples, the potassium feldspar flotation employs a closed-loop flotation process consisting of a roughing, scavenging, and cleaning step.

[0030] In some embodiments, the degree of mineral monomer liberation of the grinding slurry is greater than or equal to 90%.

[0031] In some embodiments, the weight percentage of minerals with a particle size of -200 mesh in the grinding slurry is 60% to 80%.

[0032] In some embodiments, the mass concentration of the slurry to be processed is 30% to 35%.

[0033] In some examples, the sedimentation desliming method includes at least one of two-stage natural sedimentation desliming and two-stage tandem hydrocyclone desliming.

[0034] In some embodiments, the fluorine-free separation of feldspar and quartz in the reprocessing tailings to obtain feldspar concentrate and quartz concentrate includes: adding sulfuric acid to the reprocessing tailings to adjust the pH of the slurry to 2.0-2.5, then adding dodecylamine and sodium petroleum sulfonate for roughing to obtain feldspar roughing concentrate and feldspar roughing tailings; refining the feldspar roughing concentrate to obtain the feldspar concentrate; and scavenging the feldspar roughing tailings to obtain the quartz concentrate.

[0035] In some examples, the selection is performed three times, and the ore obtained from each selection is returned to the previous step in order.

[0036] For example, the step of refining the feldspar roughing concentrate to obtain the feldspar concentrate includes:

[0037] The feldspar roughing concentrate is subjected to a first refining process to obtain a first refined medium ore and a first refined concentrate; wherein, the first refined medium ore is returned to the roughing process.

[0038] The first refined concentrate is subjected to a second refinement to obtain a second refined middlings ore and a second refined concentrate; wherein the second refined middlings ore is returned to the first refined concentrate; and

[0039] The second refined concentrate is subjected to a third refined process to obtain a third refined medium ore and the feldspar concentrate; wherein the third refined medium ore is returned to the second refined process.

[0040] In some examples, the sweeping is performed twice, and the intermediate ore obtained from each sweep is returned to the previous step in sequence.

[0041] For example, the step of scavenging the feldspar roughing tailings to obtain the quartz concentrate includes:

[0042] The feldspar roughing tailings are subjected to a first scavenging process to obtain a first scavenged ore and a first scavenged concentrate; wherein the first scavenged ore is returned to the roughing process; and

[0043] The first scavenged concentrate is subjected to a second scavenging process to obtain a second scavenged concentrate and the quartz concentrate; wherein the second scavenged concentrate is returned to the first scavenging process.

[0044] In some embodiments, the amount of dodecylamine used is 200-300 g / t of raw ore.

[0045] In some examples, the amount of dodecylamine used in the coarse selection is 200-300 g / t of raw ore.

[0046] In some embodiments, the amount of sodium petroleum sulfonate used is 300-450 g / t of raw ore.

[0047] In some examples, the amount of sodium petroleum sulfonate used in the coarse selection is 300-450 g / t of raw ore.

[0048] In some examples, the weight ratio of the dodecylamine to the sodium petroleum sulfonate is 2:3.

[0049] In some embodiments, the lithium-containing kaolin ore contains 0.2% to 0.5% Li₂O, 0.1% to 0.3% Rb₂O, and 0.01% to 0.2% Cs₂O.

[0050] The beneficial effects of this disclosure are:

[0051] 1. The segmented enrichment and recovery method provided in this disclosure can maximize the comprehensive utilization of rubidium and cesium associated with the ore while prioritizing the recovery of the main mineral, lepidolite, and the flotation reagent system is simple.

[0052] 2. The segmented enrichment and recovery method provided in this disclosure can obtain qualified feldspar and quartz products, realizing the resource utilization of tailings.

[0053] 3. The segmented enrichment and recovery method provided in this disclosure has a simple process flow, a reasonable and efficient reagent system, reduces the production cost of mineral processing, has strong industrial operability, and realizes the comprehensive utilization of lithium, rubidium, and cesium in lithium-bearing kaolin ore with associated rubidium and cesium, as well as the resource-based disposal of tailings. Detailed Implementation

[0054] The technical solutions in some embodiments of this disclosure will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this disclosure, and not all embodiments. Based on the embodiments provided in this disclosure, all other embodiments obtained by those skilled in the art are within the scope of protection of this disclosure.

[0055] Unless the context otherwise requires, throughout the specification and claims, the term "comprising" is interpreted as open and encompassing, that is, "including, but not limited to".

[0056] In describing some embodiments, the expression "A and / or B" may be used. It is readily understood that "A and / or B" includes the following three combinations: A only, B only, and a combination of A and B.

[0057] In describing some embodiments, the expressions "at least one of A, B and C" and "at least one of A, B or C" may be used, both of which have the same meaning and include the following combinations of A, B and C: only A, only B, only C, a combination of A and B, a combination of A and C, a combination of B and C, and a combination of A, B and C.

[0058] Example 1

[0059] This embodiment provides a segmented enrichment and recovery method for lithium-bearing kaolin ore containing rubidium and cesium. The lithium-bearing kaolin ore used in the experiment was obtained from Jiangxi Yongcheng Lithium Industry. Its main mineral components are quartz, plagioclase, potassium feldspar, and mica (lithium-containing muscovite), of which the content of Li2O is 0.46%, the content of Rb2O is 0.20%, and the content of Cs2O is 0.044%.

[0060] The segmented enrichment and recovery method includes the following steps:

[0061] S1. Lithium-bearing kaolin ore is ground to obtain a grinding slurry with a mineral individual liberation degree of 96.5%, wherein the weight percentage of minerals with a particle size of -200 mesh is 70.0%.

[0062] S2. Two-stage natural settling desliming is used to settling and desliming the grinding slurry to obtain sand and slurry;

[0063] S3. Feed the sand into the flotation machine, add water to adjust the slurry, and obtain a slurry with a mass concentration of 35%;

[0064] S4. Add lepidolite collector to the slurry to be beneficiated, stir and aerate for lepidolite flotation, using a closed-circuit flotation process of one rougher, one scavenger, and two cleaners to obtain lithium tailings and rubidium- and cesium-containing lepidolite concentrate; wherein, by weight, the raw materials for the lepidolite collector include 45 parts of polyetheramine, 30 parts of cottonseed oil fatty acid, 5 parts of sodium hydroxide, 8 parts of glycerol, and 12 parts of sodium petroleum sulfonate; the dosage of the lepidolite collector is 550 g / t·raw ore; the preparation method of the lepidolite collector includes: mixing cottonseed oil fatty acid, sodium hydroxide, and water, with a mass ratio of cottonseed oil fatty acid to water of 1:1, and performing a saponification reaction at 80℃ for 45 min to obtain saponified fatty acid; mixing glycerol and sodium petroleum sulfonate, stirring at 80℃ for 30 min to obtain a modifier; mixing polyetheramine, saponified fatty acid, and modifier at a mass ratio of 1:1:0.25, and stirring for 30 min to obtain the final product;

[0065] S5. Add potassium feldspar collector to lithium tailings, stir and aerate for potassium feldspar flotation, using a closed-circuit flotation process of roughing, scavenging and cleaning, to obtain re-selected tailings and rubidium-cesium-containing potassium feldspar concentrate; wherein, by weight, the potassium feldspar collector includes 50 parts soybean oil oleic acid, 15 parts white oil, 5 parts sodium hydroxide, 20 parts tributyl phosphate and 10 parts polypropylene glycol monobutyl ether; the dosage of potassium feldspar collector is 250 g / t raw ore;

[0066] S6. Add sulfuric acid to the tailings to adjust the slurry pH to 2.2, then add dodecylamine and sodium petroleum sulfonate in a mass ratio of 2:3 for roughing to obtain feldspar roughing concentrate and feldspar roughing tailings; wherein, the dosage of dodecylamine is 200 g / t·raw ore, and the dosage of sodium petroleum sulfonate is 300 g / t·raw ore.

[0067] S7. Perform three fine-tuning processes on the feldspar roughing concentrate, and return the resulting middlings sequentially to the previous stage to obtain feldspar concentrate; perform two scavenging processes on the feldspar roughing tailings, and return the resulting middlings sequentially to the previous stage to obtain quartz concentrate.

[0068] The results showed that in the rubidium-cesium-containing lepidolite concentrate, the Li₂O grade was 2.37%, the Rb₂O grade was 0.71%, and the Cs₂O grade was 0.18%, with recoveries of 75.85%, 58.12%, and 68.25%, respectively; in the rubidium-cesium-containing potassium feldspar concentrate, the K₂O grade was 6.09%, the Li₂O grade was 0.37%, the Rb₂O grade was 0.27%, and the Cs₂O grade was 0.037%, with recoveries of 27.38%, 12.03%, 22.45%, and 14.25%, respectively; in the quartz concentrate, the SiO₂ grade was 95.6%; and in the feldspar concentrate, the K₂O grade was 1.60% and the Na₂O grade was 6.52%.

[0069] Example 2

[0070] This embodiment provides a segmented enrichment and recovery method for lithium-bearing kaolin ore containing rubidium and cesium. The lithium-bearing kaolin ore used in the experiment was obtained from Yichun Times New Energy Resources Co., Ltd., and its main mineral components are quartz, plagioclase, potassium feldspar, and mica (lithium-bearing muscovite), of which the content of Li2O is 0.34%, the content of Rb2O is 0.17%, and the content of Cs2O is 0.033%.

[0071] The segmented enrichment and recovery method includes the following steps:

[0072] S1. Lithium-bearing kaolin ore is ground to obtain a grinding slurry with a mineral individual liberation degree of 95.0%, wherein the weight percentage of minerals with a particle size of -200 mesh is 62.4%.

[0073] S2. Two-stage natural settling desliming is used to settling and desliming the grinding slurry to obtain sand and slurry;

[0074] S3. Feed the sand into the flotation machine, add water to adjust the slurry, and obtain a slurry with a mass concentration of 34%;

[0075] S4. Add lepidolite collector to the slurry to be processed, stir and aerate for lepidolite flotation, using a closed-loop flotation process of one rougher, one scavenger, and two cleaners to obtain lithium tailings and rubidium- and cesium-containing lepidolite concentrate; wherein, by weight, the raw materials for the lepidolite collector include 50 parts of polyetheramine, 20 parts of cottonseed oil fatty acid, 5 parts of sodium hydroxide, 10 parts of glycerol, and 15 parts of sodium petroleum sulfonate; the dosage of lepidolite collector is 450 g / t of raw ore; the preparation method of the lepidolite collector is the same as in Example 1, except for the different proportions of raw materials;

[0076] S5. Add potassium feldspar collector to lithium tailings, stir and aerate for potassium feldspar flotation, using a closed-circuit flotation process of roughing, scavenging and cleaning, to obtain re-selected tailings and rubidium-cesium-containing potassium feldspar concentrate; wherein, by weight, the potassium feldspar collector includes 45 parts soybean oil oleic acid, 20 parts white oil, 5 parts sodium hydroxide, 15 parts tributyl phosphate and 15 parts polypropylene glycol monobutyl ether; the dosage of potassium feldspar collector is 200 g / t raw ore;

[0077] S6. Add sulfuric acid to the tailings to adjust the slurry pH to 2.0, then add dodecylamine and sodium petroleum sulfonate in a mass ratio of 2:3 for roughing to obtain feldspar roughing concentrate and feldspar roughing tailings; wherein, the dosage of dodecylamine is 260 g / t·raw ore, and the dosage of sodium petroleum sulfonate is 390 g / t·raw ore.

[0078] S7. Perform three fine-tuning processes on the feldspar roughing concentrate, and return the resulting middlings sequentially to the previous stage to obtain feldspar concentrate; perform two scavenging processes on the feldspar roughing tailings, and return the resulting middlings sequentially to the previous stage to obtain quartz concentrate.

[0079] The results showed that in the rubidium-cesium-containing lepidolite concentrate, the grades of Li₂O were 1.65%, Rb₂O 0.54%, and Cs₂O 0.12%, with recoveries of 75.32%, 53.36%, and 57.19%, respectively; in the rubidium-cesium-containing potassium feldspar concentrate, the grades of K₂O were 5.76%, Li₂O 0.32%, Rb₂O 0.17%, and Cs₂O 0.025%, with recoveries of 25.78%, 9.13%, 20.55%, and 17.35%, respectively; in the quartz concentrate, the SiO₂ grade was 95.3%; and in the feldspar concentrate, the K₂O grade was 1.56% and the Na₂O grade was 6.51%.

[0080] Example 3

[0081] This embodiment provides a segmented enrichment and recovery method for lithium-bearing kaolin ore containing rubidium and cesium. The lithium-bearing kaolin ore used in the experiment was obtained from a lithium mica mine in Africa. The main mineral components are quartz, plagioclase, potassium feldspar, and mica (lithium-bearing muscovite), wherein the content of Li2O is 0.50%, the content of Rb2O is 0.21%, and the content of Cs2O is 0.065%.

[0082] The segmented enrichment and recovery method includes the following steps:

[0083] S1. Lithium-bearing kaolin ore is ground to obtain a grinding slurry with a mineral individual liberation degree of 95.3%, of which the weight percentage of minerals with a particle size of -200 mesh is 67.5%.

[0084] S2. A two-stage series hydrocyclone group is used to deslim the grinding slurry to obtain sand and slime.

[0085] S3. Feed the sand into the flotation machine, add water to adjust the slurry, and obtain a slurry with a mass concentration of 33%;

[0086] S4. Add lepidolite collector to the slurry to be beneficiated, stir and aerate for lepidolite flotation, using a closed-loop flotation process of one rougher, one scavenger, and two cleaners to obtain lithium tailings and rubidium- and cesium-containing lepidolite concentrate; wherein, by weight, the raw materials for the lepidolite collector include 45 parts of polyetheramine, 30 parts of cottonseed oil fatty acid, 10 parts of sodium hydroxide, 5 parts of glycerol, and 10 parts of sodium petroleum sulfonate; the dosage of lepidolite collector is 600 g / t of raw ore; the preparation method of the lepidolite collector is the same as in Example 1, except for the different proportions of raw materials;

[0087] S5. Add potassium feldspar collector to lithium tailings, stir and aerate for potassium feldspar flotation, using a closed-circuit flotation process of roughing, scavenging and cleaning, to obtain re-selected tailings and rubidium-cesium-containing potassium feldspar concentrate; wherein, by weight, the potassium feldspar collector includes 47 parts soybean oil oleic acid, 16 parts white oil, 7 parts sodium hydroxide, 15 parts tributyl phosphate and 15 parts polypropylene glycol monobutyl ether; the amount of potassium feldspar collector used is 300 g / t raw ore;

[0088] S6. Add sulfuric acid to the tailings to adjust the slurry pH to 2.0, then add dodecylamine and sodium petroleum sulfonate in a mass ratio of 2:3 for roughing to obtain feldspar roughing concentrate and feldspar roughing tailings; wherein, the dosage of dodecylamine is 280 g / t·raw ore, and the dosage of sodium petroleum sulfonate is 420 g / t·raw ore.

[0089] S7. Perform three fine-tuning processes on the feldspar roughing concentrate, and return the resulting middlings sequentially to the previous stage to obtain feldspar concentrate; perform two scavenging processes on the feldspar roughing tailings, and return the resulting middlings sequentially to the previous stage to obtain quartz concentrate.

[0090] The results showed that in the rubidium-cesium-containing lepidolite concentrate, the Li₂O grade was 2.45%, the Rb₂O grade was 0.75%, and the Cs₂O grade was 0.31%, with recoveries of 79.43%, 58.02%, and 77.35%, respectively; in the rubidium-cesium-containing potassium feldspar concentrate, the K₂O grade was 6.89%, the Li₂O grade was 0.35%, the Rb₂O grade was 0.31%, and the Cs₂O grade was 0.045%, with recoveries of 34.26%, 10.21%, 21.57%, and 10.10%, respectively; in the quartz concentrate, the SiO₂ grade was 97.3%; and in the feldspar concentrate, the K₂O grade was 1.47% and the Na₂O grade was 7.02%.

[0091] Compare with Example 1

[0092] Example 1 and Comparative Example 1 were compared. The difference between Comparative Example 1 and Example 1 is as follows:

[0093] The flotation sequence was changed from lepidolite flotation-potassium feldspar flotation to potassium feldspar flotation-lepidolite flotation;

[0094] Other conditions, such as the selection and amount of remaining reagents, as well as the steps and parameters of the method, are the same as in Example 1 (compared to Example 1, this comparative example changes the order of execution of lepidolite flotation and potassium feldspar flotation to demonstrate that the segmented enrichment and recovery method of this disclosure is more effective).

[0095] The results showed that in the rubidium-cesium-containing lepidolite concentrate, the Li₂O grade was 1.68%, the Rb₂O grade was 0.61%, and the Cs₂O grade was 0.147%, with recoveries of 79.21%, 66.49%, and 72.57%, respectively; in the rubidium-cesium-containing potassium feldspar concentrate, the K₂O grade was 5.88%, the Li₂O grade was 0.34%, the Rb₂O grade was 0.28%, and the Cs₂O grade was 0.038%, with recoveries of 25.37%, 6.27%, 11.94%, and 7.34%, respectively; in the quartz concentrate, the SiO₂ grade was 92.4%; and in the feldspar concentrate, the K₂O grade was 2.08% and the Na₂O grade was 5.98%.

[0096] It can be seen that, compared with Example 1, the lithium grade and recovery rate in the rubidium- and cesium-containing lepidolite concentrate obtained in Comparative Example 1 decreased significantly. This indicates that changing the execution order of lepidolite flotation and potassium feldspar flotation will seriously affect the effect of lepidolite flotation, thus failing to obtain high-quality lepidolite concentrate.

[0097] Compare with Example 2

[0098] Example 1 and Comparative Example 2 were compared. The difference between Comparative Example 2 and Example 1 is as follows:

[0099] Replace the polyetheramine in the lepidolite collector with the same weight of cocoylamine;

[0100] Other conditions, such as the selection and dosage of the remaining reagents, as well as the steps and parameters of the method, are the same as in Example 1 (compared to Example 1, this comparative example replaces the polyetheramine in the raw material of the lepidolite collector with coconut oil amine to demonstrate that the segmented enrichment and recovery method of this disclosure is more effective).

[0101] The results showed that in the rubidium-cesium-containing lepidolite concentrate, the grades of Li₂O were 0.86%, Rb₂O 0.25%, and Cs₂O 0.048%, with recoveries of 11.51%, 7.66%, and 6.70%, respectively; in the rubidium-cesium-containing potassium feldspar concentrate, the grades of K₂O were 4.88%, Li₂O 0.58%, Rb₂O 0.21%, and Cs₂O 0.046%, with recoveries of 20.87%, 7.07%, 5.86%, and 5.85%, respectively; in the quartz concentrate, the SiO₂ grade was 89.46%; and in the feldspar concentrate, the K₂O grade was 2.54% and the Na₂O grade was 5.97%.

[0102] It can be seen that, compared with Example 1, the lithium grade and recovery rate in the rubidium- and cesium-containing lepidolite concentrate obtained in Comparative Example 2 decreased significantly. This indicates that using polyetheramine as a cationic collector in lepidolite can significantly improve the lithium grade and recovery rate.

[0103] Compare with Example 3

[0104] Example 1 and Comparative Example 3 were compared. The difference between Comparative Example 3 and Example 1 is as follows:

[0105] The lepidol collector does not contain glycerol or sodium petroleum sulfonate.

[0106] Other conditions, such as the selection and amount of remaining reagents, as well as the steps and parameters of the method, are the same as in Example 1 (compared to Example 1, this comparative example does not add glycerol and sodium petroleum sulfonate, which is used to demonstrate that the segmented enrichment and recovery method of this disclosure is more effective).

[0107] The results showed that in the rubidium-cesium-containing lepidolite concentrate, the Li₂O grade was 1.89%, the Rb₂O grade was 0.56%, and the Cs₂O grade was 0.14%, with recoveries of 51.60%, 35.28%, and 39.87%, respectively; in the rubidium-cesium-containing potassium feldspar concentrate, the K₂O grade was 5.97%, the Li₂O grade was 0.36%, the Rb₂O grade was 0.19%, and the Cs₂O grade was 0.0037%, with recoveries of 25.68%, 7.02%, 8.55%, and 7.53%, respectively; in the quartz concentrate, the SiO₂ grade was 91.26%; and in the feldspar concentrate, the K₂O grade was 1.53% and the Na₂O grade was 6.07%.

[0108] Compare with Example 4

[0109] Example 1 and Comparative Example 4 were compared. The difference between Comparative Example 4 and Example 1 is as follows:

[0110] Glycerol was not added to the lepidolite collector;

[0111] Other conditions, such as the selection and amount of remaining reagents, as well as the steps and parameters of the method, are the same as in Example 1 (this comparative example does not add glycerol compared to Example 1, to demonstrate that the fractional enrichment and recovery method of this disclosure is more effective).

[0112] The results showed that in the rubidium-cesium-containing lepidolite concentrate, the Li₂O grade was 2.17%, the Rb₂O grade was 0.68%, and the Cs₂O grade was 0.17%, with recoveries of 68.98%, 50.17%, and 56.51%, respectively; in the rubidium-cesium-containing potassium feldspar concentrate, the K₂O grade was 6.01%, the Li₂O grade was 0.36%, the Rb₂O grade was 0.25%, and the Cs₂O grade was 0.032%, with recoveries of 26.83%, 10.76%, 17.34%, and 10.00%, respectively; in the quartz concentrate, the SiO₂ grade was 93.7%; and in the feldspar concentrate, the K₂O grade was 1.65% and the Na₂O grade was 6.44%.

[0113] Compare with Example 5

[0114] Example 1 and Comparative Example 5 were compared. The difference between Comparative Example 5 and Example 1 is as follows:

[0115] Sodium petroleum sulfonate was not added to the lepidolite collector;

[0116] Other conditions, such as the selection and amount of remaining reagents, as well as the steps and parameters of the method, are the same as in Example 1 (this comparative example does not add sodium petroleum sulfonate compared to Example 1, in order to demonstrate that the segmented enrichment and recovery method of this disclosure is more effective).

[0117] The results showed that in the rubidium-cesium-containing lepidolite concentrate, the Li₂O grade was 2.03%, the Rb₂O grade was 0.61%, and the Cs₂O grade was 0.16%, with recoveries of 58.40%, 41.05%, and 48.47%, respectively; in the rubidium-cesium-containing potassium feldspar concentrate, the K₂O grade was 5.83%, the Li₂O grade was 0.29%, the Rb₂O grade was 0.21%, and the Cs₂O grade was 0.035%, with recoveries of 24.98%, 7.80%, 13.22%, and 9.92%, respectively; in the quartz concentrate, the SiO₂ grade was 94.8%; and in the feldspar concentrate, the K₂O grade was 1.62% and the Na₂O grade was 6.49%.

[0118] The above description is merely a preferred embodiment of this disclosure. It should be understood that this disclosure is not limited to the forms disclosed herein and should not be construed as excluding other embodiments. It can be used in various other combinations, modifications, and environments, and can be altered within the scope of the concept described herein through the above teachings or techniques or knowledge in related fields. Any modifications and variations made by those skilled in the art that do not depart from the spirit and scope of this disclosure should be within the protection scope of the appended claims.

Claims

1. A method for the staged enrichment and recovery of lithium-bearing kaolin ore containing rubidium and cesium, characterized in that, include: The lithium-containing kaolin ore is ground to obtain a grinding slurry; The grinding slurry is subjected to sedimentation and desliming to obtain sand and sludge; The sediment is slurry-treated to obtain the ore slurry to be processed; The ore slurry to be beneficiated was subjected to lepidolite flotation using a lepidolite collector to obtain lithium tailings and lepidolite concentrate containing rubidium and cesium. The lithium tailings were subjected to potassium feldspar flotation using a potassium feldspar collector to obtain re-selected tailings and potassium feldspar concentrate containing rubidium and cesium. as well as The tailings were subjected to fluorine-free separation of feldspar and quartz to obtain feldspar concentrate and quartz concentrate.

2. The segmented enrichment method according to claim 1, characterized in that, The raw materials of the lepidolite collector, by weight, include 40-50 parts of polyetheramine, 20-40 parts of cottonseed oil fatty acid, 5-10 parts of sodium hydroxide, 5-10 parts of glycerol, and 10-20 parts of sodium petroleum sulfonate.

3. The segmented enrichment method according to claim 2, characterized in that, The dosage of the lepidolite collector is 300-600 g / t of raw ore.

4. The segmented enrichment method according to claim 1, characterized in that, By weight, the potassium feldspar collector comprises 40-60 parts soybean oil oleic acid, 10-20 parts white oil, 5-10 parts sodium hydroxide, 15-30 parts tributyl phosphate, and 10-20 parts polypropylene glycol monobutyl ether.

5. The segmented enrichment method according to claim 4, characterized in that, The dosage of the potassium feldspar collector is 100-300 g / t of raw ore.

6. The segmented enrichment method according to claim 1, characterized in that, The degree of liberation of the mineral monomers in the grinding slurry is greater than or equal to 90%; and / or, the weight percentage of minerals with a particle size of -200 mesh in the grinding slurry is 60% to 80%.

7. The segmented enrichment method according to claim 1, characterized in that, The mass concentration of the slurry to be processed is 30% to 35%.

8. The segmented enrichment method according to claim 1, characterized in that, The process of separating feldspar and quartz from the reprocessing tailings without fluorine to obtain feldspar concentrate and quartz concentrate includes: Sulfuric acid is added to the re-selected tailings to adjust the pH of the slurry to 2.0-2.5, and then dodecylamine and sodium petroleum sulfonate are added for roughing to obtain feldspar roughing concentrate and feldspar roughing tailings. The feldspar roughing concentrate is further refined to obtain the feldspar concentrate; and The feldspar roughing tailings are scavenged to obtain the quartz concentrate.

9. The segmented enrichment method according to claim 8, characterized in that, The dosage of the dodecylamine is 200-300 g / t of raw ore; and / or the dosage of the sodium petroleum sulfonate is 300-450 g / t of raw ore.

10. The segmented enrichment method according to any one of claims 1 to 9, characterized in that, In the lithium-containing kaolin ore, the content of Li2O is 0.2% to 0.5%, the content of Rb2O is 0.1% to 0.3%, and the content of Cs2O is 0.01% to 0.2%.